Picosecond sulfur K-edge X-ray absorption spectroscopy with applications to excited state proton transfer
Picosecond X-ray absorption (XA) spectroscopy at the S K-edge (∼2.4 keV) is demonstrated and used to monitor excited state dynamics in a small organosulfur molecule (2-Thiopyridone, 2TP) following optical excitation. Multiple studies have reported that the thione (2TP) is converted into the thiol (2...
Saved in:
Published in | Structural dynamics (Melville, N.Y.) Vol. 4; no. 4; p. 044021 |
---|---|
Main Authors | , , , , , , , |
Format | Journal Article |
Language | English |
Published |
United States
American Institute of Physics, Inc
01.07.2017
American Crystallographic Association/AIP American Crystallographic Association AIP Publishing LLC and ACA |
Subjects | |
Online Access | Get full text |
Cover
Loading…
Summary: | Picosecond X-ray
absorption (XA)
spectroscopy at
the S K-edge (∼2.4 keV) is demonstrated and used to monitor excited state dynamics in a
small organosulfur molecule (2-Thiopyridone, 2TP) following optical excitation. Multiple
studies have reported that the thione (2TP) is converted into the thiol
(2-Mercaptopyridine, 2MP) following photoexcitation. However, the timescale and photochemical
pathway of this reaction remain uncertain. In this work, time-resolved XA spectroscopy at the S K-edge is
used to monitor the formation and decay of two transient species following 400 nm
excitation of 2TP dissolved in acetonitrile. The first transient species forms within the
instrument response time (70 ps) and decays within 6 ns. The second transient species
forms on a timescale of ∼400 ps and decays on a 15 ns timescale. Time-dependent density
functional theory is used to identify the first and second transient species as the
lowest-lying triplet states of 2TP and 2MP, respectively. This study demonstrates
transient S K-edge XA spectroscopy as a sensitive and viable probe of time-evolving charge
dynamics near sulfur sites in small molecules with future applications towards studying
complex biological and material systems. |
---|---|
Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 USDOE Office of Science (SC), Basic Energy Sciences (BES) AC02-05CH11231; SC0002190; AC02-76SF00515 Present address: Center for Inorganic Analysis, Division of Metrology for Quality of Life, Korea Research Institute of Standards and Science, Daejeon 34113, South Korea. Present address: PULSE Institute, SLAC National Accelerator Laboratory, Menlo Park, CA 94025, USA. Author to whom correspondence should be addressed. Electronic mail: mkhalil@uw.edu. Present address: Pohang Accelerator Laboratory, San-31 Hyoja-dong Pohang, Kyungbuk 37673, Republic of Korea. Present address: SLAC National Accelerator Laboratory, Menlo Park, CA 94025, USA. Present address: Max-Planck Institute for Chemical Energy Conversion, Stiftstrasse 34−36, D−45470 Muülheim an der Ruhr, Germany. Present address: Linac Coherent Light Source, SLAC National Accelerator Laboratory, Menlo Park, CA 94025, USA. |
ISSN: | 2329-7778 2329-7778 |
DOI: | 10.1063/1.4983157 |